Method of desensitizing clay-coated record sheet



METHOD OF DESENSITIZING CLAY-COATED RECORD SHEET Filed Nov. 9, 1954 2 2] STATEMENT JOHN DOE 35 MAIN ADSORBENT SENSI- TIZING PARTICLES cosT SELLING PRICE 14.00 25.00 22 23 I I 26 j r \OOLORLESS qReAmc (24 COLOR REAG ANT F'GQZ 20 20 FIG. 3 L L STATEMENT STATEMENT JOHN DOE JOHN DOE 35 MAIN ST. 35 MAIN ST. COST SELLING PRICE SELLING PRICE |4.00 25.00 25.00

ORIGINAL cusToMERs COPY \25 DESENSITIZED AREA 24' 20 FIG. 4

STATEMENT JOHN DOE 35 MAIN ST.

cos'r SELLING PRICE i400 25.00 -27 INVENTORS MARJORIE J. CORMACK NED A. THACKER BY FILE COPY g j m y Qim THEIR ATTORNEYS United rates METHOD OF DESENSITIZING CLAY-COATED RECORD SHEET Marjorie J. Cormack and Ned A. Thacker, Dayton, Ohio, assignors to The National Cash Register Company, Daygttzigj Ohio, a corporation of Maryland (incorporated in 1 Application November 9, 1954, Serial No. 467,792 4 Claims. (Cl. 117-36) Reference is made to United States Letters Patent No. 2,548,366, which issued April 10, 1951, on the application of Barrett K. manifold record material sensitized with such adsorbent particles.

nd sheet is coated with a composition containing the ad- When Writing or printing pressures are on the rear surface is ruptured locally and releases the oil droplets at the pressure points, which droplets are adsorbed by the adsorbent particles on the front surface of the second sheet. This manifold system is workable with the rupturable oil-droplet-containing film.

As is Well known, it is often desirable not to have some of the data recorded on the top sheet of a manifold pack appear on certain parts of certain of the inner sheets. By this invention, the appearance of data on any 2,777,780 Patented Jan. 15, 1957 stances or substances which contribute to transparency, or colored materials to match a tinted paper.

Therefore, it is an object of this invention to provide to the drawing which accompanies and forms a part of this specification.

Of the drawing:

Fig. 1 is a representation of a three-sheet manifold form with corners of the sheets turned up to allow a designation of the coatings to be made;

Fig. 2 is a representation of the top surface of the top sheet;

Fig. 3 is a representation of the top surface of the middle sheet, showing a desensitized area; and

Fig. 4 is a representation of the top surface of a bottom sheet not desensitized.

Of the many adsorbent materials which are capable of acting as electron acceptor color-reactants, the following may be mentioned:

1. Attapulgite. 2. Kaolin. 3. Pyrophyllite.

I 4. Sodium aluminum zeolite material.

5. Bentonite.

6. Halloysite.

7. Calcium sulfate.

8. Zinc sulfate. v

9. Calcium citrate.

10. Zirconium dioxide.

11. Barium sulfate.

12. Calcium fluoride.

l3. Magnesium tri-silicate.

In addition, the attapulgite, the zeolite material, kaolin, and pyrophyllite act as oxidizers for benzoyl leuco methylene blue and Michlers hydrol. The sensitization of a sheet need not be made by one of these adsorbents alone, as mixtures of them may be used.

The adsorbent or adsorbents used are applied in fine ganic color-reactant material. I

The adsorbent surface activity of the mentioned com- Cationic quaternary ammonium salts of the follow- (a) Alkyl trimethyl ammonium chlorides of the gen eral formula R-N(CH3)3C1, where R is any long chain alkyl group higher than the octyl grou such as:

(b) Aryl trimethyl ammonium chlorides of the general formula R-N(CI-Ia)aCl, where R is an aryl. group, such (1) Benzyl trimethyl ammonium chloride (c) Dialkyl dimethyl ammonium chloride'of the general formula R2N(CH3)zCl, where R is any long alkyl group higher than the octyl group, such as:

(l) Dicoconut dimethyl ammonium chloride (2) Di-hydrogenated tallow dimethyl'ammonium chloride (3) Di-lauryl dimethyl ammonium chloride Of these quaternary ammonium salts, there also are the bromide, iodide, and acetate equivalents of the mentioned chlorides.

II. Aliphatic or aryl amine acetates, such as n-dodecylamine acetate, in which the aliphatic or aryl groups are higher than the octyl group.

III. Amines and diamines of high such as:

molecular weight,

(1) Dodecyl amine; and (2) Dodecyl diarnine.

IV. Substituted oxazoline, such as: (1) 2,4,4 trimethyl-Z-oxazoline; or V (2) 2-oleyl, 4-hydromethyl 4 methyl-Z-oxazoline.

50 pts. oil tint base vehicle composed of a mixture of linseed oil varnish and resinous binders 25 pts. 2,4,4 trimethyl-Z-oxazoline 10 pts. dodecyl trimethylamminoum chloride The oil base vehicle chosen should preferably be transparent in their films, so that the desensitizing ink will not obliterate any data previously printed in the area to be desensitized. However, if such obliteration is required, an opacifier, such as titanium dioxide, may be added. The type of oil vehicle used is chosen for the particular printing process used to apply it. Reference is made to the publication Printing and Litho Inks, by Herbert J. Wolfe, fourth edition, published by MacNair-Dorland Company, New York city, in 1949, where in chapter III a number of oil base printing ink vehicles are specified. Another publication pertaining to printing ink vehicles is chapter #3 of the publication Printing Inks, by Carleton Ellis, published by Reinhold Publishing Corporation, New York city, in 1940.

The des'ensitizing materials may be applied to the record material alone or dissolved in a volatile solvent if a printing ink vehicle is not required. The :amounts of desensitizer used are not critical in any respect except that enough should be used to substantially deactivate the active and exposed surfaces of the sensitizing particles.

Among adsorbate compounds other than 3,3 bis (pdimethylaminophenyl) G-dimethylamino phthalide which is color-reactive with the mentioned adsorbent materials are 3,3 bis (p-diethylaminophenyl) 6-diethylamino phthalide; 3,3 bis (p-dimethylaminophenyl) phthalide;

Xanthene-9, o-benzoic acid, 3,6-bis-diethylamino-9-p-nitroanilino-lactam; and

2,4 bis [p-(dimethylaminophenylazo) anilino1-6-hydroxy sym. triazine.

Referring to the drawing, Fig. 1 represents a threesheet statement form bound at the top 20, the first sheet being an original which contains an area '21 for the customers name and address; and an area 22 for the cost data and selling price data, as indicated. The rear of the first, or top, sheet is coated with a rupturable gelled hydrophilic colloid film 23, containing the droplets of oily fluid containing the color-reactant. The second sheet, which is the customers copy (Fig. 3), has on its top surface 24 the adsorbent sensitizing particles, 'but in the area 25 it has been desensitized by one or more of the specified desensitizing compounds. The rear surface 26 of the second sheet is coated with the oil-droplet-containing film, as film 23, on the rear of the front sheet. The front surface 27 of the bottom sheet is the same as surface 24 of the second sheet. The matter printed on the top sheet appears on'each of'the two undersheets ex cept in the desensitized area 25 of the second sheet. The foregoing practical example shows the simplest method of applying the invention to a business form. The desensitization may be in differently placed areas on different undersheets if desired.

The desensitizing compounds are chosen not for any reactant effect on the organic color-reactant but only for their deactivating efiect on the adsorbent. Hence they are equivalents in being highly polar, non-volatile, deactivating agents.

While the method and means of this been described in connection with a number of examples of pertinent materials, it is not intended to confine the invention to such, as there are many equivalent materials.

What is claimed is:

1. The method of deactivating portions of record material sensitized with minute particles of inorganic adsorbent electron acceptor materials which cause the formation of color in an electron donor aromatic double bond color-reactant compound adsorbed thereon, by reason of an electron donor-acceptor color reaction which converts said compound to a more highly polarized conjugated form, giving it a distinctive color, including the step of applying to selected areas of the sensitized record material, before any of the organic color-reactant is applied, highly polar, non-volatile non-colo'r-forming adsorbate material sufiicient to occupy the normally available adsorbent sites on the particles of such areas.

2. The method of claim 1 in which the highly polar deactivating adsorbate is applied as a dispersion in a fluid printing vehicle. a

3. The method of claim 1 in which the highly polar deactivating adsorbate used is substantially colorless.

4. The method of claim 1 in which the highly polar deactivating adsorbate is substantially colorless and is applied dispersed in a substantially colorless fluid printing vehicle. 

1. THE METHOD OF DEACTIVATING PORTIONS OF RECORD MATERIAL SENSITIZED WITH MINUTE PARTICLES OF INORGANIC ADSORBENT ELECTRON ACCEPTOR MATERIAL WHICH CAUSE THE FORMATION OF COLOR IN AN ELECTRON DONOR AROMATIC DOUBLE BOND COLOR-REACTANT COMPOUND ADSORBED THEREON, BY REASON OF AN ELECTRON DONOR-ACCEPTOR COLOR REACTION WHICH CONVERTS SAID COMPOUND TO A MORE HIGHLY POLARIZED CONJUGATED FORM, GIVING IT A DISTINCTIV COLOR, INCLUDING THE STEP OF APPLYING TO SELECTED AREAS OF THE SENSITIZED RECORD MATERIAL, BEFORE ANY OF THE ORGANIC COLOR-FORMING ADPLIED, HIGHLY POLAR, NON-VOLATILE NON-COLOR-FORMING ADSORBATE MATERIAL SUFFICIENT TO OCCUPY THE NORMALLY AVAILABLE ADSORBENT SITES ON THE PARTICLES OF SUCH AREAS. 